Salicylic acid and halo-substituted salicylic acid salts of oxydianiline

ABSTRACT

COMPOUNDS OF THE FORMULA   ((H3N(+)-C6H4)2-O) (((X)N,2-HO-PHENYL)-COO(-))2   IN WHICH X IS H, BR, OR CL; AND N IS 0, 1, OR 2.

United States Patent Oflice 3,770,814 SALICYLIC ACID ANDHALO-SUBSTITUTED SALICYLIC ACID SALTS F OXYDIANILINE Theodore E.Majewski, Midland, and James P. Easterly,

Bay City, Mich., assignors to The Dow Chemical Company, Midland, Mich.

No Drawing. Original application May 3, 1968, Ser. No. 726,537, nowPatent No. 3,689,536. Divided and this application Feb. 22, 1972, Ser.No. 228,358

Int. Cl. C07c 93/00 US. Cl. 260501.18 4 Claims ABSTRACT OF THEDISCLOSURE Compounds of the formula in which X is H, Br, or Cl; and n is0, l, or 2.

The compounds are useful as fungicides, insecticides, herbicides, andthe like.

This is a division of application, Ser. No. 726,537 filed May 3, l968,now U.S. Pat. No. 3,689,536.

The present invention relates to oxydianiline salts of salicyclic acidand certain halogenated salicyclic acids.

The reaction by which the compounds of this invention are prepared isthe simple neutralization reaction between the carboxyl groups ofsalicylic acid or halogenated salicylic acid and the amino groups ofoxydianiline. The reaction is preferably conducted in an inert organicsolvent, which is a solvent for both of the reactants. It may benecessary to heat the reaction mixture in order to solubilize either oneor both of the reactants. The reactants and the inert solvent are merelymixed together with stirring and heating until solution has beenachieved, and heating and stirring are continued for a period of time toinsure substantially complete reaction. The temperature used can varywidely from about room temperature to about 200 C. Solvents which permitthe use of reaction temperatures in the range of 100 C. to about 150 C.are preferred.

The reaction solvent is necessarily one which is unreactive with eitherof the reactants and is preferably one in which both reactants havesubstantial solubility. Aromatic and aliphatic hydrocarbon solvents andhalogenated hydrocarbon solvents are preferred in the preparation ofnovel compounds of this invention. Chlorobenzene and dichlorobenzene areparticularly preferred reaction solvents.

The starting reactants in the production of the compounds of thisinvention are salicylic acid, chlorinatedor brominated-salicylic acids,and oxydianiline. The substituted salicylic acids which can be used asstarting reactants are those having one or two chloro or bromosubstituents.

3,770,814 Patented Nov. 6, 1973 The preferred salicylic acid compoundsare salicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylicacid, 5- chlorosalicylic acid, and 5-bromosalicylic acid. Oxydianilinessuch as 2,2-oxydianiline, 3,3'-oxydianiline, and 4,4- oxydianiline canbe employed as the oxydianiline reactant. The preferred reactant is4,4-oxydianiline.

The oxydianiline used is preferably of high purity. The purification ofdianilines is disclosed in US. Pats. 3,175,007 to Berhenke and 3,251,880to Gentry. Oxydianilines purified by the processes described in eitherof these patents are satisfactory for use in the production of thecompounds in this invention.

The novel salicylic acid salts of oxydianiline of this invention findutility as .fungicides, herbicides, and insecticides. For instance, thesalt of 3,5-dibromosalicylic acid and 4,4'-oxydianiline is effective inthe prevention of rice blast and lettuce downy mildew when applied toplants as an aqueous dispersion of p.p.m. concentration. The salicylicacid salt of 4,4'-oxydianiline finds utility as a preemergent herbicideto control barn yard grass and rice when applied to the soil in amountsof about 10 pounds per acre. The salt of S-chlorosalicylic acid and4,4'-oxydianiline is effective as a contact insecticide against plumcurculio when applied in a spray or dust in 0.1 percent concentration orless. The S-bromosalicylic acid salt of 4,4'-oxydianiline is similarlyetfective against the American cockroach. This compound also preventstomato late blight when applied to the plants as an aqueous dispersionin concentrations of 100 p.p.m. or more.

The invention may be more fully understood by reference to the followingexamples. All parts and percentages are by weight unless otherwiseindicated. These examples are illustrative of certain embodimentsdesigned to teach those skilled in the art how to practice the inventionand to represent the best mode contemplated for carrying out theinvention and are not intended to limit the scope of the invention inany way.

EXAMPLE 1 This example illustrates the preparation of the salt of4,4-oxydianiline and 5-chlorosalicylic acid.

Purified 4,4-oxydianiline (0.05 mole, 10 g.), 5-chlorosalicylic acid(0.10 mole, 17.2 g.), and 250 ml. of chlorobenzene were charged into a500 ml. 3 neck round bottom flask equipped with a motor stirrer andreflux condenser. The reaction mixture was heated to C., at whichtemperature solution was attained. The solution was maintained, withstirring, for about 1 hour. The resulting purple solid was collected ona Biichner funnel using toluene as an aid in transferring, and then thesolid was washed with Skelly B solvent.

The salt weighed 27.5 g. and its M.P. was ISO-154 C. (uncorrected). Thematerial was dried in an electric oven for 24 hours in an effort toimprove its quality.

The M.P. was improved to 153-155 C. (uncorrected).

The results of elemental analysis were:

3 EXAMPLE 2 This example illustrates the preparation of the salt of4,4'-oxydianiline and S-brornosalicylic acid.

The procedure was identical to that of Example 1 with 4 EXAMPLE 4 Thisexample illustrates the preparation of the salt of 4,4-oxydianiline andsalicylic acid.

Following the general procedure of Examples 1-3, salithe exception thatS-bromosalicylic acid (21.7 g., 0.10 5 cylic acid and 4,4-oxydianilineare reacted to obtain the mole) was used as a substitute forS-chlorosalicylic acid expected salt. In a representative preparation,the reaction of Example 1 and 350 ml. of chlorobenzene was used mixturewas filtered and the collected product was washed as a solvent. withtoluene and dried at 65 C. to obtain a violet powder,

A total of 29 g. of a grey powder, melting at 157-158" MP. 9910l C.(uncorrected). It was identified by ele- C. (uncorrected), was obtained.This material was ideutimental analysis as the expected disalicylate ofY fied by elemental analysis as the expected salt. a line as follows:

EXAMPLE 3 This example illustrates the preparation of the salt ofPercent Found Them 4,4-oxydianiline and 3,5-dibromosalicylic acid.Carbon 65.4 65.54 A 1 liter, 3 neck round bottom flask equipped with afifgfiggggf g g: motor stirrer, a reflux condenser, and a heater wascharged with 10 g. (0.05 mole) of 4,4-oxydianiline and 29.1 g. (0.10mole) of 3,5-dibromosalicylic acid and 500 ml. of Y the proceduredescribed 11 e above p e e o-dichlonobenzene. The reaction mixture washeated with can be p i 1 Salts 0f lsPmel'lc OXYdIB-BIHHBS stirring at150 C. for about 1 hour. The contents were Q-"Q Y Y Y then allowed tocool at room temperature with continued 311111116) W Othef halogenatedfi l y a01dS i-g, stirring. The resulting solid was collected on aBiichner bromosalfcylfc acld, G'ChIOI'OSaIICYhC acid, f n l, h d i h Skl B Solvent 0 00 C), and chlorosalicyhc acid, and 4,6-dichlorosalicylicacid). These d i d i an electric oven at 30 salts have propertiessimilar to those of the closely related A grey powder weighing 36 g.melted with decomposisalts of the examplestio at 207 203 (unconfined;Elemental analysifi Although the invention has been illustrated inconsiderwas as f ll able detail with reference to certain preferredembodimerits, it will be understood that variations and modificap m;Found Theory tions can be effected within the spirit and scope of thein- Carbon 39. a 43 v fl'on as described above and as defined in theappended gisdrogen. clalmsrogeu- .54 What is claimed is B 3 9 w 39 1. Acompound selected from the group consisting of 0- Q t 0 H ct c1 0H h Q-Q J 0.

Br Br and Br Br Br -Br 2. The compound of claim 1 having the formula b-oL0 3,77 0,814 5 3. The compound of claim 1 having the .formula Br Br 4.The compound of claim 1 having the formula fi I References Cited UNITEDSTATES PATENTS 3,682,968 8/1972 Shen et a1 260--501.17 X

LEON ZITVER, Primary Examiner M. W. GLYNN, Assistant Examiner

